CN114433860A - Micron-scale succulent porous iron-cobalt alloy and preparation and application thereof - Google Patents

Micron-scale succulent porous iron-cobalt alloy and preparation and application thereof Download PDF

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CN114433860A
CN114433860A CN202111576060.4A CN202111576060A CN114433860A CN 114433860 A CN114433860 A CN 114433860A CN 202111576060 A CN202111576060 A CN 202111576060A CN 114433860 A CN114433860 A CN 114433860A
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succulent
cobalt alloy
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iron
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CN114433860B (en
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车仁超
杨子琪
张捷
熊旭辉
游文彬
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Fudan University
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    • B22F9/20Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C19/07Alloys based on nickel or cobalt based on cobalt
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    • C22C38/10Ferrous alloys, e.g. steel alloys containing cobalt
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Abstract

The invention relates to a micron-scale succulent porous iron-cobalt alloy, and preparation and application thereof. The stable vortex domain structure can improve the magnetic storage capacity, and the violent movement of the magnetic moment is beneficial to improving the magnetic loss capacity, so that the material has higher complex permeability. The porous structure increases multiple scattering and optimizes impedance matching. Therefore, compared with the prior art, the fleshy iron-cobalt alloy material has the effective absorption bandwidth of 5.7GHz, the maximum reflection loss of-53.8 dB and excellent electromagnetic wave loss capability in the frequency range of 2.0-18.0 GHz.

Description

Micron-scale succulent porous iron-cobalt alloy and preparation and application thereof
Technical Field
The invention belongs to the technical field of functional material preparation, and relates to a micron-scale succulent porous iron-cobalt alloy, and preparation and application thereof.
Background
With the rapid development of scientific technology and the arrival of the information age, various electronic devices and electronic devices have been closely related to our lives. People can not ignore the increasingly serious problems of electromagnetic interference, electromagnetic pollution and the like while enjoying the convenience brought by the users. The use of electronic devices in industrial and domestic environments has increased the number of electromagnetic wave emitting and receiving sources, which causes electromagnetic interference and pollution, which not only affects the normal use of electronic devices, but also may harm the health of human beings and other living organisms. Microwave absorbing materials have been developed to reduce electromagnetic interference and pollution. The loss mechanism of the wave-absorbing material to the electromagnetic wave is mainly divided into magnetic loss taking a magnetic medium as a main factor and dielectric loss taking a dielectric medium and an electric conductor as a main factor. The magnetic material has the characteristics of a double loss mechanism and the like, and is widely applied to the field of electromagnetic wave absorption. Magnetic transition metals and alloy materials, such as iron, cobalt, nickel, iron-cobalt alloys, and the like, have intrinsic ferromagnetic properties, such as strong saturation magnetization, high curie temperature, spontaneous magnetization, magnetocrystalline anisotropy, and the like, and are beneficial to dissipation of electromagnetic waves and improvement of microwave absorption performance.
FeCo alloys are important soft magnetic materials of metals, and are receiving attention due to their unique properties such as high saturation magnetic induction, low coercive force, high magnetic permeability, and low magnetic anisotropy constant. The excellent properties enable the iron-cobalt alloy to be widely applied to a plurality of fields such as magnetic recording materials, wave-absorbing materials, biotechnology, catalytic catalyst materials, hard alloy materials and the like. However, the existing iron-cobalt alloy wave-absorbing material is generally of a non-porous structure and the like, and the performance of the material in the aspects of electromagnetic wave absorption and the like still has a larger improvement space.
Disclosure of Invention
The invention aims to provide a micron-scale succulent porous iron-cobalt alloy, and preparation and application thereof.
It has been found through research that single-component magnetic metal or alloy materials as microwave absorbers still face several obstacles. For example, the disadvantages of narrow absorption bandwidth, reduced reflection attenuation, and thick coating prevent their practical application. In addition, the magnetic nanoparticles currently studied have size limitations and a single magnetic domain structure, and generally show relatively weak magnetic loss. In contrast, the assembly of the magnetic transition metal alloy material can realize adjustable anisotropy, change the topological structure of the magnetic domain and be beneficial to improving the complex permeability. Based on the method, the micron-scale succulent porous iron-cobalt alloy material is prepared. By adjusting the hydrothermal reaction time during preparation of the precursor, the microstructure of the iron-cobalt alloy can be greatly changed, and the structure can influence the electromagnetic parameters and impedance matching characteristics of the material, so that the purpose of accurately regulating and controlling the wave absorption performance of the magnetic material is finally achieved. The stable combination of a plurality of vortex domains is beneficial to improving the magnetic storage capacity and the magnetic loss capacity and enhancing the attenuation capacity of the iron-cobalt alloy to electromagnetic waves.
The invention adopts an efficient and simple hydrothermal reaction method to synthesize the precursor cobalt iron oxyhydroxide. After high-temperature reduction in the hydrogen-argon atmosphere, the product particles have good dispersibility and do not have obvious agglomeration phenomenon. Meanwhile, the succulent porous iron-cobalt alloy shows excellent comprehensive performance in the field of microwave absorption.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a preparation method of a micron-scale succulent porous iron-cobalt alloy, which comprises the following steps:
(1) adding ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ammonium fluoride and urea into deionized water, and stirring for dissolving to obtain a transparent light pink mixed solution;
(2) transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction, washing and drying the obtained reaction product to obtain orange precursor powder;
(3) and (3) placing the precursor powder in a hydrogen argon atmosphere for high-temperature reduction, and then cooling to room temperature to obtain the target product.
Further, in the step (1), the molar ratio of the ferric nitrate nonahydrate to the cobalt nitrate hexahydrate to the ammonium fluoride to the urea is (1-3): (1-4): (4-10): (12-18).
Further, in the step (1), the addition amount of the deionized water satisfies the following condition: fe in the mixed solution3+The concentration is 0.01-0.03 mol/L.
Further, in the step (2), the temperature of the hydrothermal reaction is 80-140 ℃ and the time is 40-80 min.
Further, in the step (2), the washing process is as follows: and adopting deionized water and ethanol to centrifugally wash for several times at the rotating speed of 8000-10000 rpm.
Further, in the step (2), the drying process specifically comprises: and (3) drying in vacuum at the temperature of 60-80 ℃.
Further, in the step (3), the volume fraction of hydrogen in the hydrogen argon atmosphere is 4-6%.
Further, in the step (3), the high-temperature reduction process specifically comprises: calcining for 1-3 h at 550-650 ℃.
The second technical scheme of the invention provides a micron-scale succulent porous iron-cobalt alloy which is prepared by the preparation method, the porous iron-cobalt alloy is succulent, the size of the porous iron-cobalt alloy is about 2-3 mu m, and a nano-pore structure is distributed on the surface of the porous iron-cobalt alloy.
The third technical scheme of the invention provides application of the micron-scale succulent porous iron-cobalt alloy which is used as a microwave absorbing material. In particular as an electromagnetic wave absorbing material. When the method is applied specifically, the steps are as follows: the prepared iron-cobalt alloy powder and the sliced paraffin are uniformly mixed in a mass ratio of 1: 1. The mixture was poured into an aluminum mold and pressed into a circular ring sample having an inner diameter of 3.0mm, an outer diameter of 7.0mm and a thickness of 2.0 mm. The complex relative permittivity and permeability in the range of 2.0-18.0GHz was tested using a vector network analyzer model N5230C.
Compared with the prior art, the micron-scale succulent porous iron-cobalt alloy has the characteristics of high absorption strength and wide response frequency band, and the magnetic storage capacity is improved because the center of a vortex domain moves slightly along with a magnetic field and a domain wall is basically stable; and magnetic vectors near the domain wall vibrate violently, so that the magnetic material has strong natural resonance and domain wall resonance effects, and the magnetic loss capability is improved. The strong magnetic coupling effect between the structural units improves the complex magnetic conductivity and enhances the magnetic loss. The rich pore structure increases multiple scattering and multiple reflection, further optimizing impedance matching. The micron-scale succulent porous iron-cobalt alloy has good electromagnetic wave absorption performance, strong magnetism and easy preparation, and has good application prospect.
Drawings
FIG. 1 is a scanning electron micrograph and a transmission electron micrograph of examples 1 to 4: (a1) example 1-scanning electron micrograph of succulent iron-cobalt alloy; (a2) example 1-transmission electron micrograph of succulent iron-cobalt alloy; (b1) example 2 scanning electron micrograph of spherical iron-cobalt alloy; (b2) example 2 transmission electron micrograph of spherical iron-cobalt alloy; (c1) example 3-scanning electron micrograph of near-fleshy iron-cobalt alloy; (c2) example 3 transmission electron micrograph of near fleshy iron-cobalt alloy; (d1) example 4-scanning electron micrograph of fleshy iron-cobalt alloy; (d2) example 4-transmission electron micrograph of excessively fleshy iron-cobalt alloy.
FIG. 2 is an X-ray diffraction pattern of the succulent Fe-Co alloy of example 1.
FIG. 3 is the relative complex permeability, including real and imaginary parts, of example 1, a succulent Fe-Co alloy.
FIG. 4 is the relative complex permittivity, including real and imaginary parts, of the complex permittivity for example 1-succulent iron-cobalt alloy.
FIG. 5 shows the values of the reflection loss at a thickness of 2.0mm for examples 1 to 4.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, unless otherwise specified, the starting materials or the treatment techniques are all conventional and commercially available materials or conventional treatment techniques in the art.
Example 1:
preparing a micron-scale succulent porous iron-cobalt alloy:
first, 1mmol of Fe (NO) was weighed out separately3)3·9H2O,3mmol Co(NO3)2·6H2O,8mmol NH4F,15mmol CO(NH2)2And adding the mixture into 50mL of deionized water, and completely dissolving the mixture under the condition of vigorous magnetic stirring to obtain a uniform and transparent light pink solution.
The solution was then transferred to a teflon lined stainless steel hydrothermal reaction kettle and heated at 120 ℃ for 1 hour. Cooling to room temperature, centrifugally washing with deionized water and ethanol for several times, vacuum drying at 60 ℃, and collecting orange FexCo1-xOOH precursor.
Finally, the precursor powder is placed in a porcelain boat and is put into a tube furnace to be reduced for 2 hours at the high temperature of 600 ℃ under the atmosphere of hydrogen and argon (the volume fraction of hydrogen is 5 percent), and the heating rate is 2 ℃/min-1Naturally cooling to room temperature to obtain the micron-scale porous iron-cobalt alloy black powder. The shape of the nano-porous membrane is similar to a fleshy shape, the size of the nano-porous membrane is about 2-3 mu m, and the nano-porous membrane has a uniformly distributed nano-porous structure on the surface.
Example 2:
compared to example 1, most of them are the same except that in this example: the hydrothermal reaction time was changed to 20 minutes.
Example 3:
compared to example 1, most of them are the same except that in this example: the hydrothermal time was 40 minutes.
Example 4:
compared to example 1, most of them are the same except that in this example: the hydrothermal time was 80 minutes.
The microstructure of the micron-scale succulent porous iron-cobalt alloy with controllable morphology in the above example was characterized by scanning electron microscopy (SEM, Hitachi FE-SEM S-4800), and a powder sample was coated on the surface of the conductive paste for testing. The microstructure information of a series of alloy materials is characterized by a transmission electron microscope (TEM, JEOL JEM-2100F), and a powder sample is ultrasonically dispersed in ethanol and then dropped on a carbon-supported copper net for drying to test. The X-ray diffraction spectra were measured by a bruker d8 Advance instrument. And (3) testing the complex relative permeability and the complex relative dielectric constant within the range of 2.0-18.0GHz by using a vector network analyzer with the model number of N5230C, and obtaining the reflection loss values under different thicknesses through calculation and fitting.
FIG. 1 is a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM) of the synthesized fleshy porous Fe-Co alloy of the above examples 1-4, and as shown in the figure, the morphology of example 1 is similar to fleshy, the size is about 2-3 μm, and the surface has a uniformly distributed nano-pore structure. The sample has uniform particle size distribution and good particle dispersibility. Example 2 is spherical-like in morphology, about 2-3 μm in size, and has a uniformly distributed nanoporous structure on the surface. Compared with example 1, example 2 does not evolve into fleshy due to the shortened hydrothermal time, and the magnetic domain structure is relatively single. Example 3 morphology resembles the unformed fleshy, about 2-3 μm in size, with a uniformly distributed nanoporous structure on the surface. Example 4 morphology resembles an overcooked fleshy, with dimensions of about 2-3 μm, nanopores with larger pore sizes than examples 1-3, and surface cracks. Therefore, the hydrothermal reaction time is an important condition for morphology evolution.
FIG. 2 is an X-ray diffraction (XRD) analysis of the succulent porous Fe-Co alloy of example 1. In the figure, diffraction peaks at 2 θ 44.75 °,65.13 °, and 82.45 ° correspond to the (110), (200), and (211) crystal planes of simple cubic FeCo (JCPDS No. 49-1567). XRD pattern analysis proves the component information of the material, and no obvious impurity and miscible phase exist.
FIG. 3 is a graph showing the real part of complex permeability (. mu.) and the imaginary part of complex permeability (. mu.) of the succulent porous Fe-Co alloy of example 1 to reveal the mechanism of its excellent wave absorption property (. mu.')rμ' -j μ "). The succulent iron-cobalt alloy has a plurality of stable vortex domains, and compared with the spherical porous iron-cobalt alloy in example 2, the value of mu' is improved to a certain extent, which indicates that the magnetic storage capacity is improved. Under the alternating magnetic field, the magnetic moment near the domain wall vibrates more intensely and is connected with the surrounding vortex domain, so that the mu' value and the magnetic loss capability are improved.
FIG. 4 is a graph showing the real part (. epsilon. ') and imaginary part (. epsilon. ') of the complex permittivity of the succulent porous Fe-Co alloy of example 1 to reveal the mechanism of its excellent wave-absorbing property (. epsilon. ')r═ epsilon' -j epsilon "). The wave absorbing performance of the material mainly derives from the conductivity loss and polarization loss capability. Compared with the spherical porous iron-cobalt alloy in the embodiment 2, under the same filler ratio, because the volume of single succulent particles is increased, the connection between samples in a paraffin matrix is reduced, and epsilon' of the succulent iron-cobalt alloy is reduced to a certain degree, which is beneficial to realizing better impedance matching, thereby improving the wave-absorbing performance of the succulent porous iron-cobalt alloy.
FIG. 5 shows the values of the reflection loss in the frequency range of 2.0 to 18.0GHz at a thickness of 2.0mm in examples 1 to 4. As shown in the figure, when the thickness of the sample of the succulent porous iron-cobalt alloy is 2.0mm, the maximum reflection loss value reaches-53.8 dB, and the effective absorption bandwidth is 5.7 GHz. Example 2-spherical porous Fe-Co alloy when the sample thickness is 2.0mm, the maximum reflection loss value reaches-16.4 dB, and the effective absorption bandwidth is 3.6 GHz; example 3-near succulent iron cobalt alloy when the sample thickness is 2.0mm, the maximum reflection loss value reaches-23.8 dB, and the effective absorption bandwidth is 5.1 GHz; example 4-the maximum reflection loss value of the excessively fleshy iron-cobalt alloy reaches-13.5 dB at a sample thickness of 2.0mm, and the effective absorption bandwidth is 2.6 GHz. Under the same thickness, the microwave absorption performance of the examples 2-4 is lower than that of the example 1-succulent porous iron-cobalt alloy, which shows that the hydrothermal reaction time is an important condition for regulating and controlling electromagnetic parameters to further influence the wave absorption performance. The multi-meat-shaped porous iron-cobalt alloy with the micron scale simultaneously meets the practical application requirements of strong absorption, broadband response and thin thickness, and is a potential high-efficiency wave-absorbing material.
Example 5:
compared to example 1, most of them are the same except that in this example:
the addition amount of the ferric nitrate nonahydrate, the cobalt nitrate hexahydrate, the ammonium fluoride and the urea has the molar ratio of 3: 1: 8: 15, Fe3+The concentration was 0.06 mol/L.
Example 6:
compared to example 1, most of them are the same except that in this example:
the addition amount of the ferric nitrate nonahydrate, the cobalt nitrate hexahydrate, the ammonium fluoride and the urea has the molar ratio of 1: 1: 8: 15, Fe3+The concentration is 0.02 mol/L.
Example 7:
compared to example 1, most of them are the same except that in this example:
the mol ratio of the addition amounts of the ferric nitrate nonahydrate, the cobalt nitrate hexahydrate, the ammonium fluoride and the urea is 1: 1: 4: 15, Fe3+The concentration is 0.02 mol/L.
Example 8:
compared to example 1, most of them are the same except that in this example:
the addition amount of the ferric nitrate nonahydrate, the cobalt nitrate hexahydrate, the ammonium fluoride and the urea has the molar ratio of 2: 4: 10: 15.
example 9:
most of the same is true as in example 1, except that the hydrothermal reaction temperature is adjusted to 140 ℃ in this example.
Example 10:
most of the same was obtained as in example 1, except that the hydrothermal reaction temperature was adjusted to 80 ℃ in this example.
Example 11:
most of them were the same as in example 1, except that in this example, the temperature of the high-temperature reduction was adjusted to be 550 ℃ for calcination for 3 hours.
Example 12:
most of them were the same as in example 1, except that in this example, the temperature of the high-temperature reduction was adjusted to calcination at 650 ℃ for 1 hour.
Example 13:
compared with example 1, most of them were the same except that in this example, the volume fraction of hydrogen in the hydrogen-argon atmosphere was 4%.
Example 14:
compared with example 1, most of them were the same except that in this example, the volume fraction of hydrogen in the hydrogen-argon atmosphere was 6%.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A preparation method of a micron-scale succulent porous iron-cobalt alloy is characterized by comprising the following steps:
(1) adding ferric nitrate nonahydrate, cobalt nitrate hexahydrate, ammonium fluoride and urea into deionized water, and stirring for dissolving to obtain a transparent light pink mixed solution;
(2) transferring the mixed solution into a reaction kettle, carrying out hydrothermal reaction, washing and drying the obtained reaction product to obtain orange precursor powder;
(3) and (3) placing the precursor powder in a hydrogen argon atmosphere for high-temperature reduction, and then cooling to room temperature to obtain the target product.
2. The method for preparing the micron-scale succulent porous iron-cobalt alloy according to claim 1, wherein in the step (1), the molar ratio of the iron nitrate nonahydrate to the cobalt nitrate hexahydrate to the ammonium fluoride to the urea is (1-3): (1-4): (4-10): (12-18).
3. The preparation method of the micron-scale succulent porous iron-cobalt alloy as claimed in claim 1, wherein in the step (1), the addition amount of deionized water satisfies the following condition: fe in the mixed solution3+The concentration is 0.01-0.03 mol/L.
4. The method for preparing a micron-sized succulent porous Fe-Co alloy according to claim 1, wherein in the step (2), the temperature of the hydrothermal reaction is 80-140 ℃ and the time is 40-80 min.
5. The method for preparing the micron-scale succulent porous iron-cobalt alloy according to claim 1, wherein in the step (2), the washing process is as follows: and adopting deionized water and ethanol to centrifugally wash for several times at the rotating speed of 8000-10000 rpm.
6. The method for preparing the micron-scale succulent porous iron-cobalt alloy according to claim 1, wherein in the step (2), the drying process specifically comprises the following steps: and (3) drying in vacuum at the temperature of 60-80 ℃.
7. The method for preparing the micron-scale succulent porous iron-cobalt alloy according to claim 1, wherein in the step (3), the volume fraction of hydrogen in the hydrogen-argon atmosphere is 4-6%.
8. The preparation method of the micron-scale succulent porous iron-cobalt alloy as claimed in claim 1, wherein in the step (3), the high-temperature reduction process specifically comprises: calcining for 1-3 h at 550-650 ℃.
9. The micron-scale succulent porous iron-cobalt alloy is prepared by the preparation method according to any one of claims 1 to 8, and is characterized in that the porous iron-cobalt alloy is succulent, 2-3 μm in size and nano-pore structures are distributed on the surface of the porous iron-cobalt alloy.
10. Use of a micro-scale succulent porous Fe-Co alloy according to claim 9 as microwave absorbing material.
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